-------
in the ABS emulsion process. The vent emissions from the batch reactors are
highly variable with changing compositions. Most of these vents are
controlled by a flare.
Butadiene emissions also occur during the coagulation and dewatering
stages and from intermediate process latex tanks. Only one facility uses a
control device and this is limited to one of the downstream vents which is
controlled by routing the vent to the plant boiler; others vent to the
atmosphere. Figure 11 shows the process vent locations: Vent A for
emissions directly associated with the process and Vent B for emissions from
a control device.
Equipment Leaks--
The estimates for uncontrolled equipment leaks at the two facilities
appearing in Table 22 are based on equipment counts provided by the
facilities. The estimation procedure is described in Appendix A. One
location reports daily inspection of equipment; however, no further details
on follow up for any leaks discovered during these inspections are given.
NITRILE ELASTOMER PRODUCTION
Nitrile elastomer or nitrile-butyl rubber (NBR) is produced by seven
21
facilities, with an eighth due to begin production by the end of 1988.
The location of the facilities, the type of elastomer produced, and their
approximate capacities are presented in Table 23.
Nitrile elastomer is considered a specialty elastomer and is primarily
used for its oil, solvent, and chemical resistant properties by a variety of
22
manufacturers. Some uses include hose, belting, and cable manufacturing,
and molded goods such as seals and gaskets. Nitrile elastomer production
2
accounts for about 3 percent of total annual butadiene consumption.
Several of the facilities involved in NBR production also produce other
elastomers. Goodyear in Texas, Polysar in Tennessee, Copolymer, and
81
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TABLE 23. NITRILE ELASTOMER PRODUCTION FACILITIES
21
Company
Copolymer
B. F. Goodrich
Goodyear
Goodyear
Polysar, Ltd.
Polysar Latex Division
Reichhold Chemicals
Uni royal Chemical Co.
Location
Baton Rouge, LA
Louisville, KY
Houston, TX
Akron, OH
Orange, TX
Chattanooga, TN
Cheswold, DE
Painesville, OH
Elastomer Type
Unknown
Solid rubber
Solid rubber
Solid rubber,
latex
Solid rubber
Latex
Latex
Solid rubber
Capacity (Mg/yr
dry rubber or
latex) in 1988
6,000
32,500
23,000
6,000
l,600a
5,000
5,000
20,000
Due on line by the end of 1988.
82
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Reichhold all produce styrene-butadiene copolymers. The Polysar facility in
Orange, Texas, due to begin nitrile elastomer production in 1988, already
produces polybutadiene. Because of the common use of butadiene in these
production processes, emissions data often represent total rather than
individual process emissions. Whenever possible, the portion of butadiene
emissions directly attributable to nitrile rubber is shown.
Process Description
Nitrile elastomers are copolymers of acrylonitrile and butadiene. They
are produced by emulsion polymerization in batch or continuous processes.
20
The process is illustrated in the block flow diagram, Figure 14.
The emulsion polymerization process uses water as a carrier medium.
Butadiene and acrylonitrile monomers are piped to agitated polymerization
reactors (Step 1) along with additives and soap. The water not only serves
as a reaction medium, but also effectively transfers the heat of reaction to
the cooled reactor surfaces. The additives include a catalyst (cumene
hydroperoxide as an oxidizing component), sodium formaldehyde sulfoxylate
with EDTA (ferrous sulfate complexed with ethylenediamine-tetraacetic acid)
as the reducing component, and modifiers (alky! mercaptans).
The reaction is allowed to proceed for 5 to 12 hours. A shortstop
solution (sodium bisulfate or potassium dimethyl dithiocarbonate) is added
to terminate the reaction at a predetermined point, usually after 75 to
90 percent conversion (depending upon the desired molecular weight of the
product). The reaction latex is then sent to a blowdown tank (Step 2) where
antioxidants are normally added.
The latex is subjected to several vacuum flash steps (3) where most of
the unreacted butadiene is released. It is then steam stripped under vacuum
(Step 4) to remove the remaining butadiene and most of the unreacted
acrylonitrile. The unreacted monomers are sent to recovery and recycle.
Stripped latex at about 110 to 130°F is pumped to blend tanks (Step 5).
83
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Gases released in the flash steps and stripped overhead contain
butadiene. These are sent to a partial condenser (not shown) and separator
(Step 6) where butadiene vapor is condensed and sent to liquid storage.
Uncondensed butadiene vapor from the separator flows to an absorber
(Step 7) where it is absorbed by countercurrent contact with chilled oil.
The absorber bottoms are pumped to a flash tank (not shown) and dissolved
butadiene is released and returned to the compressor. The hot lean oil is
then cooled, chilled, and returned to the top of the absorber.
Unreacted acrylonitrile in flash vapors and latex stripper overhead is
recovered by sending these gases to a water absorber (Step 8). Absorber
bottoms and the liquid phase of the latex stripper overhead are pumped to a
steam stripper (Step 9). The overhead vapor stream from this stripper is
condensed in a decanter. Phase separation is allowed to take place and the
acrylonitrile phase is decanted to storage while the water-rich phase with
residual acrylonitrile is returned to the stripper.
Latex is pumped from the blend tanks (Step 5) to a coagulation tank
(Step 10) where the emulsion is broken by the addition of dilute inorganic
salt solution (sodium chloride or aluminum sulfate) or a weak organic acid.
The slurry of fine polymer crumb is then filtered to remove coagulating
chemicals (liquor is recycled) and may be reslurried for further
purification. Crumb is dewatered in an extruder (Step 11), then hot air
dried (Step 12). Dried rubber is weighed, pressed into bales, and prepared
for shipment.
If latex is the desired end product, the final processing steps
(coagulation, screening, washing, and drying) are omitted. The initial
19
steps are essentially identical to those for solid rubber production.
Emissions
The availability of emissions data is somewhat limited. At
coproduction facilities, the estimated butadiene emissions include releases
from other elastomer production processes. For the two facilities which are
85
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also SB copolymer producers, the percent of the total reported emissions
assigned to the NBR process is based on the percent of total production
resulting in nitrile elastomer in 1984. Table 24 summarizes emissions
information for process vents, equipment leaks, and secondary sources. All
19
nitrile elastomer production is assumed to be operating at full capacity.
Emissions from emergency and accidental releases and transfer/handling are
not known and storage vent emissions from butadiene storage are expected to
be low because of the use of tanks under pressure.
Process Vent Emissions--
All six facilities for which emissions data were reported use some
level of emissions control. Many of the controls which are designed to
reduce acrylonitrile emissions are also effective in reducing butadiene
emissions (for example, flares). Data from four of these are summarized as
emission factor ranges in Table 24 (see Tables B-21 and B-22 in Appendix B
for facility-specific data). The fifth is not used because calculation of
an emission factor might reveal company confidential information on
production capacity. Potential vent locations shown in Figure 14 as Vent A
are based on information on the vent locations supplied by five facilities.
The emission factor ranges have been developed as described in
Section 4.0. The facility emission factor range includes the various levels
of control that each facility has in place. The uncontrolled emission
factor range represents, potential emissions if controls were not in use.
The units shown are in kilograms butadiene emitted per megagram of product
(kg/Mg) and the English unit equivalents (Ibs/ton) appear in parentheses.
Equipment Leaks--
The estimates for equipment leaks provided by three facilities span
three orders of magnitude (Table 24). The only known control devices
currently in use are rupture discs and a flare for pressure relief devices
by one facility. The other three facilities indicate daily visual
inspection of equipment; however, no repair programs are described for any
86
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of the leaks found. Although some controls are in place, detailed
information to apply during emissions estimation was not available.
Therefore, only calculations for potential emissions have been done. These
are in units of megagram butadiene emitted per year (Mg/yr) with English
unit equivalents (tons/yr) given In parentheses.
Secondary Emissions--
One emissions estimate from secondary sources of 60 kg/yr was
19
provided. This estimate includes the following sources: wastewater,
solid waste, and contaminated cooling water. A second facility also
19
indicated wastewater and solid waste as potential secondary sources. The
butadiene content in the wastewater is undetermined, therefore, emissions
cannot be estimated. However, the solid waste stream contains 4 ppm
butadiene. Based on a generation rate of 1063 Ibs/day and assumptions of
continuous operation and total volatilization, the source's emission
23
potential is approximately 20 kg/yr.
88
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REFERENCES FOR SECTION 5
1. Memorandum from R. A. Wassel and K. Q. Kuhn, Radian Corporation, to the
Butadiene Source Category Concurrence File, April 8, 1986. Estimates
of 1,3-Butadiene Emissions from Styrene-Butadiene Copolymer Facilities
and Emissions Reductions Achievable with Additional Controls.
2. Chemical Profile: Butadiene. Chemical Marketing Reporter,
233(15):55-56. 1988.
3. Shreve's Chemical Process Industries. McGraw-Hill Book Company, New
York, New York. 1984. p. 701.
4. SRI International. 1987 Directory of Chemical Producers - U.S.A.
Menlo Park, California. 1987.
5. Chemical Profile: SB Rubber. Chemical Marketing Reporter, 227(17):54.
1985.
6. Chemical Profile: Polybutadiene. Chemical Marketing Reporter,
233(21):50. 1988.
7. Memorandum from E. P. Epner, Radian Corporation, to the Butadiene
Source Category Concurrence File, March 27, 1986. Estimates of
1,3-Butadiene from Polybutadiene Facilities and Emissions Reductions
Achievable with Additional Controls.
.8. Memorandum from E. P. Epner, Radian Corporation, to the Butadiene
Source Category Concurrence File, May 5, 1986. Estimates for
Short-term Emissions of 1,3-Butadiene from Polybutadiene Production
Facilities.
9. Mark, H. F., et al., eds. Kirk-Othmer Concise Encyclopedia of Chemical
Technology. John Wiley and Sons, Inc., New York, New York. 1985.
p. 789.
10. U. S. Department of Health and Human Services. Industrial Hygiene
Walkthrough Survey Report of E.I. DuPont de Nemours Company, Sabine
River Works, Orange, Texas. OHHS (NIOSH) Publication No. 1W/147.32
(PB86-223203). National Institute for Occupational Safety and Health,
Cincinnati, Ohio. 1986 (August 27, 1985 Survey).
11. Letter and attachments from J. M. Stall ings, E. I. DuPont, to
J. R. Farmer, U. S. EPA, July 27, 1984. Response to questionnaire on
butadiene emissions for adiponitrile process and dodecanedioic acid
process at Victoria, Texas.
12. Memorandum from K. Q. Kuhn and R. C. Burt, Radian Corporation, to the
Butadiene Source Category Concurrence File, December 12, 1986.
Estimates of 1,3-Butadiene Emissions from Miscellaneous Sources and
Emissions Reductions Achievable with Candidate NESHAP Controls.
89
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13. Johnson, P. R. Neoprene. (In) Encyclopedia of Chemical Technology,
3rd ed. Volume 8. R. E. Kirk, et al., eds. John Wiley and Sons,
New York, New York. 1979. p. 521.
14. Chemical Profile: Neoprene. Chemical Marketing Reporter, 227(18):58.
1985.
15. Memorandum from E. P. Epner, Radian Corporation, to L. B. Evans, U. S.
EPA/Chemicals and Petroleum Branch, December 23, 1985. Estimates of
1,3-Butadiene Emissions from Neoprene Facilities and Emissions
Reductions Achievable with Additional Controls.
16. Johnson, P. R. Chloroprene. (In) Encyclopedia of Chemical Technology,
3rd ed. Volume 5. R. E. Kirk, et al., eds. John Wiley and Sons, New
York, New York. 1979. pp. 773-785.
17. Memorandum from E.P. Epner, Radian Corporation, to the Butadiene Source
Category Concurrence File, April 7, 1986. Estimates of Short-term
Emissions of 1,3-Butadiene from Neoprene/Chloroprene Production
Facilities.
18. Chemical Profile: ABS Resins. Chemical Marketing Reporter,
233(14):48, 50. 1988.
19. Memorandum from R. Burt and R. Howie, Radian Corporation, to
L. B. Evans, EPA/Chemicals and Petroleum Branch, January 29, 1986.
Estimates of Acrylonitrile, Butadiene, and Other VOC Emissions and
Controls for ABS and NBR Facilities.
20. -Energy and Environmental Analysis, Inc. Source Category Survey for the
Acrylonitrile Industry - Draft Report. ABS/SAN Operations: Emissions
and Control Data. Prepared for U. S. EPA. 1981. Cited in reference
19.
21. Chemical Profile: Nitrile Rubber. Chemical Marketing Reporter,
233(20):50. 1988.
22. Robinson, H. W. Nitrile Rubber. (In) Encyclopedia of Chemical
Technology, 3rd ed. Volume 8. R. E. Kirk, et al., eds. Wiley and
Sons, New York, New York. 1979. p. 534.
23. Letter and attachments from R. C. Niles, Uniroyal Chemical Company,
to J. R. Farmer, U. S. EPA, September 4, 1984. Response to EPA
questionnaire on butadiene emissions from the NBR process at
Painesville, Ohio.
90
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SECTION 6
BUTADIENE EMISSIONS FROM MOBILE SOURCES
This section summarizes recent work by the Office of Mobile Sources
which has quantified butadiene as one component of vehicle hydrocarbon
emissions. Butadiene emissions are formed in vehicle exhaust by the
incomplete combustion of the fuel. As a rule, refiners try to minimize the
level of butadiene in gasoline and diesel fuel because it tends to readily
form a varnish which can be harmful to engines. Therefore, the majority of
gasoline and diesel fuel should have no significant butadiene content. As a
result, it is assumed that butadiene is not present in vehicle evaporative
or refueling emissions.
Recent work by the U. S. EPA Office of Mobile Sources (QMS) on the
percent butadiene in vehicle exhaust hydrocarbon emissions refines previous
estimates made by this office. The new percent, 0.35 percent, is based on
data from light-duty, three-way catalyst-equipped vehicles. In the absence
of reliable test data for other vehicle classes, QMS applied this percent to
MOBILES-predicted exhaust hydrocarbon emission factors for all vehicle
classes to obtain butadiene emission factors. These are given in Table 25.
Based on the limited data available, butadiene emissions appear to
increase roughly in proportion to hydrocarbon emissions. Since hydrocarbon
emissions from noncatalyst-equipped vehicles are greater than their
catalyst-equipped counterparts, butadiene emissions are expected to be
higher from noncatalyst-equipped vehicles.
91
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TABLE 25. VEHICLE EMISSION FACTORS FOR 1,3-BUTADIENE EMISSIONS1
Vehicle Class
Light-duty Gas Vehicle
Light-duty Gas Truck
Heavy-duty Gas Vehicle
Heavy-duty Diesel Vehicle
Emission
1980
0.0127
0.0205
0.0328
0.0159
Factors fq butadiene/mi
1995 a
No I/M*
0.0041
0.0087
0.0089
0.0086
le driven)
1995
With I/M
0.0028
0.0055
0.0089
0.0086
aI/M means inspection and maintenance program.
92
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REFERENCES FOR SECTION 6
1. Memorandum from P. M. Carey, U. S. EPA/Office of Mobile Sources, to
T. F. Lahre, U. S. EPA/Office of Mr Quality Planning and Standards,
Nonpriority Pollutant Branch, May 24, 1988. 1,3-Butadiene Emission
Factors.
93
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SECTION 7
EMISSIONS FROM MISCELLANEOUS SOURCES OF BUTADIENE
This section provides an overview of the miscellaneous sources of
butadiene emissions. These sources may be divided into three categories:
butadiene use in manufacturing, indirect sources, and "other." With regard
to the first category, Section 5 already discusses the major uses of
butadiene; this section identifies the smaller consumers that account for
about two percent of butadiene use in the United States. Available details
of the production process and associated emissions will be provided, where
known. Often these details are incomplete; therefore, readers should
contact the facilities directly for the most accurate information.
Information on indirect sources (that is, processes that produce
butadiene as a by-product or where butadiene appears as an impurity) is
limited and any associated emission estimates are even more scarce. A few
stationary sources, however, have been identified and are described briefly
in the second half of this section.
The third category, "other," encompasses situations where butadiene may
be present as an impurity which may, therefore, be potential butadiene
sources. However, these could not be classified otherwise for lack of
readily available information.
MISCELLANEOUS USES OF BUTADIENE IN CHEMICAL PRODUCTION
Eighteen companies at 20 locations are producing 14 different products
from butadiene. Originally identified in a summary report on miscellaneous
butadiene uses, this list has been updated using the 1987 Directory of
Chemical Producers - U.S.A. These facilities are summarized in Table 26,
along with estimated capacities. Because data corresponding to each
location are not readily available, all the production process descriptions,
95
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current as of 1984, appear first, followed by a summary of any emissions
estimates.
Product and Process Descriptions
Styrene-Butadiene-Vinylpyridine (SBV) Latex--
No information on the production process or use of styrene-butadiene-
vinylpyridine latex 1s available. As a copolymer, the production is likely
to be similar to that of other copolymers.
Tetrahydrophthalic (THP) Anhydride and Acid--
Tetrahydrophthalic anhydride and acid (the acid is the hydrate form of
the chemical) may be used either as a curing agent for epoxy resins or as an
intermediate in the manufacture of Captan®, an agricultural fungicide.
In the manufacture of the anhydride as a curing agent, Mobay Synthetics
(formerly Denka) is reported to use the following process. Liquid butadiene
is first pressure fed to a vaporizer. The resulting vapor is then pressure
fed to the reactor where reaction with molten maleic anhydride occurs.
Maleic anhydride is consumed over a period of 6 to 10 hours. The product,
molten THP anhydride, is crystallized onto a chill roller at the bagging
operation. Solidified anhydride is cut from the roller by a doctor blade
A
into a weighed container, either a bag or drum. Because ArChem also uses
THP anhydride in epoxy resins, use of a process similar to Mobay
Synthetics' is assumed.
Calhio was reported to generate the anhydride for captive use as an
intermediate for Captan*. In the generation process, butadiene is charged
to reactors along with maleic anhydride to produce THP anhydride. The
reaction is a Diels-Alder reaction run under moderate temperature and
pressure.
98
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Butadiene-Vinylpyridine Latex--
Butadiene-vinylpyridine latex is produced at the B. F. Goodrich, Akron,
Ohio facility as an ingredient in an adhesive promoter. As a copolymer, the
production process is similar to that of other copolymers, usually involving
an emulsion polymerization process. B. F. Goodrich operates the process in
a batch mode, on a schedule that depends on demand.
The finished latex is blended with SB latex and a phenol-formaldehyde
mixture to form a "dip" or an adhesive promoter. Dip is used with fabrics
in geared rubber goods manufacturing. This includes fabric use in tires,
hoses, and belting production.
Methyl Methacrylate-Butadiene-Styrene (MBS) Terpolymers--
Methyl methacrylate-butadiene-styrene terpolymers are produced in resin
form by four companies at four locations. This resin is used as an impact
modifier in rigid polyvinyl chloride products for applications in packaging,
building, and construction.
Production of MBS terpolymers is achieved using an emulsion process in
which methyl methacrylate and styrene are grafted onto a styrene-butadiene
rubber. The product is a two-phase polymer.
Captan*--
In Captan* production, tetrahydrophthalic anhydride is passed through
an ammonia scrubber to produce tetrahydrophthalimide (THPI). Molten THPI is
coated onto a chill roller where it solidifies into a quasi-crystalline
state.
Tetrahydrophtalimide is then conveyed into a reactor containing
perch!oromethyl mercaptan (PMM). Caustic is charged to the reactor
initiating the reaction that produces Captan*. Captan* is brought to a
99
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higher temperature in the heat treatment tank to remove residual PMM, after
which the material passes through a vacuum filter to remove salt and water.
The product cake is dried and collected in a baghouse.
Captafol*--
Chevron produces Captafol*, a fungicide, under the trade name
Difolatan® at their Richmond, California facility. The only information on
the process is that production occurs on a continuous basis and is carried
out in a pressurized system vented to an incinerator.
1,4-Hexadiene--
DuPont produces 1,4-hexadiene for use in manufacturing Nordel*
synthetic rubber. Nordel* polymer is used in the manufacture of rubber
goods, wire and cable insulation, automotive bumpers, and as an oil
g
additive.
In the reactor, butadiene reacts with ethylene to form 1,4-hexadiene.
After reaction, unreacted 1,3-butadiene and ethylene, along with
1,4-hexadiene and by-products, are flashed from the catalyst and solvent.
The maximum temperature in the process is approximately 250°F. The catalyst
solution is pumped back to the reactor; vaporized components are sent to a
stripper column. The column separates ethylene and 1,3-butadiene from the
1,4-hexadiene product and by-products; unreacted components are pumped back
to the reactor. The 1,4-hexadiene and by-products are sent to crude product
storage before transfer to refining. The 1,4-hexadiene is refined in
low-boiler and high-boiler removal columns and transferred to the "Nordel®"
polymerization process.
Dodecanedioic Acid (DDDA)--
Dodecanedioic acid is produced by DuPont to use as an intermediate in
the production of 1,5,9-cyclodecatriene, a constituent in the manufacture of
g
OuPont's Quiana* fabric. Butadiene can be converted into several
100
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different cyclic or open chain dimers and trimers depending upon the
reaction conditions and catalysts. Although vinylcyclohexene and
1,5-cyclooctadiene are the predominant products, 1,2-divinylcyclobutane may
be formed under suitable reaction conditions. Nickel catalysts are often
used in the cyclodimerization and cyclotrimerization of butadiene; however,
complexes of iron, copper (I), zeolite, and compositions also promote
q
cyclodimerization, often giving cyclooctadiene as the principal product.
Butadiene Cylinders--
Phillips Chemical Company fills cylinders with butadiene monomer at
their Borger, Texas, facility. The NIOSH survey report on this facility
indicates that these cylinders may be samples of butadiene taken for process
quality control. The report describes routine quality control sampling in
the tank farm area in which the samples are collected using pressure
cylinders. Operators connect the sample containers to a process line and
open valves to fill the cylinder. Butadiene fills the container and is
purged out of the rear of the cylinder before the valve is closed, resulting
in emissions from the cylinder. The sample container is subjected to vacuum
exhaust under a laboratory hood at the conclusion of sampling.
Butadiene Furfural Cotrimer--
Butadiene furfural cotrimer or 2,3,4,5-bis(butadiene)tetrahydrofur-
fural, commonly known as R-ll, is used as an insect repel! ant and as a
delousing agent for cows in the dairy industry. The concentrations of R-ll
in commercial insecticide spray is generally less than one percent.
Production of R-ll at the Phillips' Borger, Texas, facility, occurs
intermittently throughout the year; however, when operating, the production
process is a continuous operation. In the process, butadiene reacts with an
excess of furfural in a liquid-phase reactor. The reaction proceeds under
moderate conditions of temperature and pressure and consumes 1 mole of
furfural for 2 moles of butadiene. After a period of 4 to 5 hours, the
101
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reaction mixture is transferred to the reactor effluent surge tank. The
mixture proceeds to a vertical column that separates butadiene dimer by
distillation. Butadiene dimer, or 4-vinyl-l-cyclohexane, is recovered from
the column and later transported to a refinery for reprocessing in crude
catalytic cracking units.
Furfural is removed from the reaction products by distillation in a
similar column and recycled to the reactor. The last column in the R-ll
process runs as a batch operation, and separates R-ll from the polymer
kettle product. The kettle product 1s a crystalline solid which 1s disposed
of in an on-site landfill. R-ll, which is in the form of a yellow liquid,
is transferred to storage tanks and shipped to customers in drums.
Sulfolane--
Sulfolane is a trade name for tetrahydrothiophene-l,l-dioxide. It is
used principally as a solvent for extracting aromatic hydrocarbons from
mixtures containing straight-chained hydrocarbons. Sulfolane is produced by
first reacting butadiene and sulfur dioxide to form 3-sulfolene. The
3-sulfolene is then hydrogenated to produce Sulfolane. Phillips Chemicals'
Borger, Texas, facility is assumed to be using a similar process since it is
listed in Reference 2 as also producing Sulfolene. The Shell facility at
Norco, Louisiana, has a Sulfolane production unit downstream of the
butadiene recovery process that is included as part of the butadiene
production facility.
Methyl Methacrylate-Acrylonitrile-Butadiene-Styrene (MABS) Polymers--
Methyl methacrylate-acrylonitrile-butadiene-styrene polymers are
produced by Standard Oil Company under the trade name Barex". The MABS
copolymers are prepared by dissolving or dispersing polybutadiene rubber in
a mixture of methyl methacrylate-acrylonitrile-styrene and butadiene
monomer. The graft copolymerization is carried out by a bulk or a
102
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suspension process. The final polymer 1s two phase, with the continuous
phase terpolymer of methyl methacrylate, acrylonltrlle, and styrene grafted
onto the dispersed polybutadlene phase.
These polymers are used in the plastics industry in applications
requiring a tough, transparent, highly impact-resistant, and thermally
formable material. Except for their transparency, the MABS polymers are
similar to the opaque acrylonitrile-butadiene-styrene plastics. The primary
function of methyl methacrylate is to match the refractive indices of the
two phases, thereby imparting transparency.
Butadiene Dimers--
Tetrahydrobenzaldehyde (THBA), a butadiene dimer, is produced by Union
Carbide, DuPont (Victoria, Texas) and Pony Industries. At Union Carbide,
butadiene is reacted with acrolein and cyclohexane to produce THB anhydride
in 90+ percent yields over a short period of time when the reaction is
carried out at temperatures up to 200°C. The reaction will also take
place at room temperature in the presence of an aluminum-titanium catalyst.
12
A by-product of the reaction is 4-vinyl-l-cyclohexane. At Union Carbide's
facility, THBA is recovered and the unreacted raw materials are recycled to
the feed pot. The feed pot, reactor, recovery stills, and refined product
storage tanks are all vented to a flare header. In the absence of process
information at the DuPont and Pony Industries facilities, they are assumed
to be using a similar production process.
Ethylidene Norbornene (ENB)--
Ethylidene norbornene, produced by Union Carbide, is a diene used as a
third monomer in the production of ethylene-propylene-dimethacrylates.
Ethylene-propylene-dimethacrylate elastomers are unique in that they are
always unsaturated in the side chain pendant to the main or backbone chain.
Therefore, any oxidation or chemical reaction with residual unsaturation has
only a limited effect on the properties of the elastomer.
103
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Emissions
No emissions data are available for the following products: SBV latex,
Captan*, Captafol*, THP Acid, and Ethylidene Norbornene. For processes
where emissions information is available, it is limited to three sources:
process vents, equipment leaks, and secondary sources. ' Butadiene
emissions from raw material storage are expected to be negligible since
butadiene is usually stored under pressure. Some emissions resulting from
accidental and emergency releases and transfer and handling of raw materials
are likely; however, they have not generally been quantified.
Data are available for process vent emissions from eight production
processes. At five of these facilities, flares or boilers are used on some
vents to control emissions. At a sixth facility, emissions reduction is
achieved by recovery of the vented stream off the butadiene-furfural
cotrimer process, one of the two process vents identified. Because every
facility did not report an emissions estimate for each process vent listed,
emissions data are incomplete.
The emission factors for process vents and secondary sources are
summarized as ranges in Table 27, with facility-specific data appearing in
Tables B-23 through B-25 in Appendix B. The facility emission factor range
includes the various levels of control that each facililty has in place.
The uncontrolled emission factor range represents potential emissions if
controls were not in use. The units shown are in kilograms butadiene
emitted per megagram of product (kg/Mg) with the English unit equivalents
(Ibs/ton) appearing in parentheses.
Because equipment count data were not readily available, no
calculations of equipment leak emissions using average CMA factors was done.
Instead, emissions as reported in the summary memoranda are shown here.
Equipment leaks were estimated for eight processes at eight facilities.
Using equipment counts grouped according to the percent butadiene in the
streams, the time in service for each component, and EPA emission factors
104
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TAKE 27. SUMMARY Of EMISSION FACTORS FOR MISCELLANEOUS CHEMICALS PRODUCTION FACILITIES1'6'11
Chesrical Produced
Butadiene cylinders
Butadiene diners
Butadiene-furfural cot rimers
Sutadiene-vinylpyridine latex
Dodecanedioic acid
1,4-hexadiene
Methy Imethacry 1 ate- but ad i ene-
styrene resina
Sulfolane
Tetrahydropnthalie anhydride/acid
Source
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leeks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leeks
Secondary Sources
(Uestewater)
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Source*
Process Vents
Equipment Leaks
Secondary Sources
Process Vents
Equipment Leaks
Secondary Sources
Facility Emission Factors*'6
21.6 kg/Ng (43.2)
<0.1 Mg/yr (<0.11)
Not reported
0.015 kg/Mg (0.030)
3.9 Mg/yr (4.3)
0
220 kg/Mg (440)
0.5 Mg/yr (1.1)
0
c
0.55 Mg/yr (0.61)
c
5.2 Mg/yr V<5.73)
Not reported
c
53.3 Mg/yr (59.3)
0
0.9 kg/Mg (1.8)
3.6 - 15.3 Mg/yr (4.0-17.4)
(n«2)
0 (n»2)
1.6 • 13.3 Mg/yr (1.3-14.7)
Not reported
Not reported
2.2 Mg/yr (2.4)
0 (n»2)
Uncontrolled Emission Factors'
21.6 kg/Mg (43.2)
<0.1 Mg/yr (<0.11)
0.77 kg/Mg (1.54)
Not available
0
220 kg/Mg (440)
Not available
0
c
Not available
5.2 Mg/yr (5.73)
c
61.4 Mg/yr (67.7)
a
3.6 kg/Mg (17.2)
15.3 Mg/yr, (17.4)
not reported (n=2)
0 (n»2)
1.6 - 13.3 Mg/yr (1.3-14.7)
2.2 Mg/yr (2.4)
0 (n=2)
Assumes production capacity * 100 percent. Values are in units of kg butadiene emitted per Mg product or, in the case of
equipment leeks, Mg butadiene emitted per year. The numrs in parentheses are in units of pounds butadiene emitted per ton
product (Ibs/ton) or tons butadiene emitted per year (tons/yr).
Ranges are basad on actual emissions reported by the facilities. Thus, values include controls whenever they have been
implemented.
Sot calculated because production capacity «as not available.
105
-------
(see Table 8), the procedure outlined in Appendix A was followed. Because
Information on emissions control through leak detection and repair programs
is incomplete, adjustments to estimated emissions cannot be made. The only
other controls in use were double mechanical pump seals and rupture discs on
pressure relief devices. The emissions are in units of megagrams butadiene
emitted per year (Mg/yr) and the equivalents in English units (tons/yr) are
given in parentheses.
Based on information on secondary sources from eight facilities,
emissions generally appear to be negligible from these sources, despite
different end products. One exception is the butadiene-vinylpyridine
process. The facility has estimated butadiene emissions from wastewater
volatilization to be approximately 1.2 Mg/yr.
Two estimates for emergency vent releases during upsets, startups, and
shutdowns of the 1,4-hexadiene process are as follows: 0.2 Mg/yr
(uncontrolled) off the abatement collection system for waste liquid and
vapors and 43.1 Mg/yr from the reactor emergency vent. A brine refrigerated
condenser on the reactor emergency vent may afford some emissions reduction
but an efficiency has not been indicated.
OTHER POTENTIAL BUTADIENE SOURCES
Specific information on indirect sources is limited to vinyl chloride
monomer (VCM) and polyvinyl chloride (PVG) production processes. In VCM
production, butadiene appears as an impurity in the final product at a
14
maximum level of 6.0 parts per million (ppm). An emission factor
developed for overall production of PVC at a representative plant has been
calculated and is given as 21 x 10" grams butadiene per kilogram PVC
produced.
Some estimates for emissions from wastewater sent to POTWs by SB
copolymer producers, considered a secondary source, have been made based on
three industry responses to EPA Section 114 requests. Using data on the
106
-------
butadiene content of wastewater sent to a POTW for each of these facilities
and air emission models developed by EPA's Office of Air Quality Planning
and Standards (OAQPS) for treatment, storage and disposal facilities
estimated emissions for all three are 19 Mg/yr. This approach did not
account for volatilization from wastewater during transport to the POTW.
Other potential sources have been identified by OAQPS which has
collected information to assist State and local agencies in their air toxic
programs. One document "Toxic Air Pollutant/Source Crosswalk: A Screening
Tool for Locating Possible Sources Emitting Toxic Air Pollutants" provides
a list of possible sources for a number of toxic air pollutants. The
Standard Industrial Classification (SIC) Codes identified in the report as
possible butadiene sources are shown in Table 28.
Data collected by NIOSH during the 1972-1974 National Occupational
17 18
Health (NOH) survey ' identifies additional potential emission sources
which are also listed in Table 28. The work was designed specifically to
estimate the number of workers potentially exposed to butadiene grouped by
SIC Code. In some cases the "potential exposure" determination was
supported by observing butadiene in use. However, many of these cases are
based on trade name product use; that is, the product used was derived from
butadiene or may otherwise have a potential to contain butadiene.
19
In a second, more recent NOH survey, 1981-1983, six additional
industries were identified as posing a potential for worker exposure. These
are also included in Table 28. Because many SIC Codes have been revised,
the one used in the study is given in parentheses after the SIC Code under
which the catergory would be classified in 1989.
It is important to remember that these data were collected by NIOSH to
assess worker exposure. These do not necessarily translate directly into
atmospheric emission sources due to possible in-plant controls and butadiene
removal as a result of its reactivity. However, the lists represent several
107
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TABLE 28. POTENTIAL SOURCE CATEGORIES OF BUTADIENE EMISSIONS
1987 SIC Cod**
1987 Description
2269*
2273 (2272")
2621***
2631**
2652
2672***
2812*
2813***
2818***
2819
2851
2865*
2869*
2879*
2899
2911***
2951
2992***
2999***
3011
3021*
3052* (3041)
3069b (3031)
308. 3432 (3079)
3357
3494
3499b
3533
Dyeing and finishing of textiles, except wool fabrics and unit-finishers of textiles,
not elsewhere classified
Carpets and rugs
Paper and allied products • paper Mills
Paperfaoard art Us
Paperboard containers and boxes - set up paper-board boxes
Converted paper and paperboard products, except containers and boxes - coated and
laminated paper, not elsewhere classified
Industrial inorganic chemicals - alkalis and chlorine
Industrial inorganic chemicals - industrial gases
Industrial inorganic chemicals - inorganic pigments
Industrial inorganic chemicals - not elsewhere classified
Paints, varnishes, lacquers, enamels, and allied products
Cyclic organic crudes and intermediates, and organic dyes and pigments.
Industrial organic chemicals, not elsewhere classified
Pesticides and agricultural chemicals, not elsewhere classified
Chemicals and chemical preparations, not elsewhere classified
Petroleun refining
Asphalt paving and roofing materials - paving mixtures and blocks
Miscellaneous products of petroleum and coal - lubricating oils and greases
Products of petroleum and coal - not elsewhere classified
Rubber and miscellaneous plastics products - tires and inner tubes
Rubber and plastics footwear
Rubber and plastics hose and belting
Fabricated rubber products - not elsewhere classified
Miscellaneous plastics products, plumbing fixtures fitting and trim
Nonferrous wire drawing and insulating
Miscellaneous fabricated metal products - valves and pipe fittings, not elsewhere
classified
Fabricated metal products, not elsewhere classified
Construction, mining, and material .handling machinery and equipment - oil and gas
field machinery
108
-------
TABLE 28. (Continued)
1987 SIC Codt"
1987 Description
3569 General industry machinery and equipment - net elsewhere classified
3585 Air-conditioning and warm air heating equipment and coMaercial and industrial
refrigeration equipment
3621*** Electrical industrial apparatus • Motors and generators
36(3 Electric lighting and wiring equipment • current-carrying wiring devices
3651 Household audio and video equipment
3721 Aircraft and parts - aircraft
3799 Transportation equipment - not elsewhere classified
3841 Surgical and medical instruments and apparatus
3996 Linoleum, asphalted felt-base, and other hard surface floor coverings - not elsewhere
classified
4226* Special warehousing and storage, not elsewhere classified
4231*** Terminal and joint maintenance facilities for motor freight transportation
4612*** Pipelines, except natural gas - crude petroleum pipelines
5014** Motor vehicles and motor vehicle parts and supplies - tires and tubes
5162, 5169 Chemicals and allied products - plastic materials and (5161*) basic forms and shapes,
not elsewhere classified
5171*** Petroleum and petroleum products - petroleum bulk stations and terminals
5541 Gasoline service stations
6513 Real estate operators - apartment buildings
7319 Advertising - not elsewhere classified
7538** Automotive repair shops - general
306 Hospitals
8372, 8741-8743 Commercial economic, sociological, and educational research, management, and public
8748 (7392) relations services except facilities support
8731 (7391**) Research, development and testing services - commercial physical and biological research
8734*** Research, development, and testing services - testing laboratories
aThose without an asterisk are from the MIOSH MOH 1972-1974 survey. The SIC Code in parentheses is the one
used in the study, but it has since changed.
b3IC Code is listed by both EPA and MIOSH.
*SIC Code is listed as a potential source in the EPA "Crosswalk" document, Reference 16.
"SIC Code was identified as possible butadiene source during the NIOSH NOH 1981-1983 survey.
***SIC Code was identified from the Toxic Release Chemical Inventory Database for 1987 submittals by
industry, Reference 19.
109
-------
possible sources that may not otherwise be immediately Identified as having
a butadiene emissions potential.
A fourth reference for butadiene sources was the Toxic Chemical Release
19
Inventory Data Base. Industry reporting of butadiene releases for 1987
were identified by SIC Code and are included in Table 28.
110
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REFERENCES FOR SECTION 7
1. Memorandum from K. Q. Kuhn and R. C. Burt, Radian Corporation, to the
Butadiene Source Category Concurrence File, December 12, 1986.
Estimates of 1,3-Butadiene Emissions from Miscellaneous Sources and
Emission Reductions Achievable with Candidate NESHAP Controls.
2. SRI International. 1987 Directory of Chemical Producers - U.S.A.
Menlo Park, California. 1987.
3. SRI International. 1986 Directory of Chemical Producers - U.S.A. and
Supplement 1. Menlo Park, California. 1986.
4. U. S. Department of Health and Human Services. Industrial Hygiene
Walk-through Survey Report of Denka Chemical Corporation, Houston,
Texas. DHHS (NIOSH) Publication No. 1W/147.27 (PB86-225406). National
Institute for Occupational Safety and Health, Cincinnati, Ohio. 1986
(July 30, 1985 Survey).
5. U. S. Department of Health and Human Services. Industrial Hygiene
Walk-through Survey Report of Calhio Chemicals, Inc., Perry, Ohio,
subsidiary of Stauffer Chemical Company, Perry, Ohio. DHHS (NIOSH)
Publication No. 1W/147.24 (PB86-224458). National Institute for
Occupational Safety and Health, Cincinnati, Ohio. 1986 (August 14,
1985 Survey).
6. Telecon. Buchanan, S. K., Radian Corporation, with Urig, E.
(July 25 1988) and Lewis, T. (July 26 1988), B. F. Goodrich. Process
description and emissions estimates.
7. Graft Copolymerization. (In) Encyclopedia of Chemical Technology,
3rd ad. Volume 15. John Wiley and Sons, New York, New York. 1978.
pp. 389-390.
8. U. S. Department of Health and Human Services. Industrial Hygiene
Walk-through Survey Report of E. I.'DuPont de Nemours Company, Beaumont
Works Facility, Beaumont, Texas. DHHS (NIOSH) Publication
No. 1W/147.33 (PB86-225380). National Institute for Occupational
Safety and Health, Cincinnati, Ohio. 1986 (August 28, 1985 Survey).
9. Diels-Alder Reactions. (In) Encyclopedia of Chemical Technology,
3rd ed. Volume 4. R. E. Kirk, et al., eds. John Wiley and Sons,
New York, New York. 1978. pp. 315-316.
10. U. S. Department of Health and Human Services. Industrial Hygiene
Survey Report of Phillips Chemical Company, Philtex Plant, Borger,
Texas, DHHS (NIOSH) Publication No. 1W/147.23 (PB86-222395). National
Institute for Occupational Safety and Health, Cincinnati, Ohio. 1986
(August 7, 1985 Survey).
Ill
-------
11. Memorandum from K. Q. Kuhn and R. A. Wassel, Radian Corporation, to the
Butadiene Source Category Concurrence File, March 25, 1986. Estimates
of 1,3-Butadiene Emissions from Production Facilities and Emissions
Reductions Achievable with Additional Controls.
12. Reference 9, pp. 314-315.
13. Ethanol as Fuel: Options, Advantages, and Disadvantages to Exhaust
Stacks, Cost. (In) Encyclopedia of Chemical Processing and Design.
Volume 20. J. J. McKetta and W. A. Cunningham, eds. Marcel Dekker,
Inc., New York, New York. 1984. pp. 343-345.
14. Khan, Z. S., and T. W. Hughes, Monsanto Research Corporation. Source
Assessment: Polyvinyl Chloride. EPA-600/2-78-004i (NTIS
PB-283395/2BE). U. S. Environmental Protection Agency, Cincinnati,
Ohio. 1978. p. 14.
15. White, T. S., Radian Corporation. Volatile Organic Compound Emissions
from Rubber Processing Facilities at Downstream POTW. Final Report.
Prepared under EPA Contract No. 68-02-4398. U. S. Environmental
Protection Agency, Research Triangle Park, North Carolina. 1987.
16. U. S. Environmental Protection Agency. Toxic Air Pollutant/Source
Crosswalk: A Screening Tool for Locating Possible Sources Emitting
Toxic Air Pollutants. EPA-450/4-87-023a. Noncriteria Pollutant
Programs Branch, Research Triangle Park, North Carolina. December
1987. p. 2-136.
17. Telecon. Buchanan, S. K., Radian Corporation, with Seta, J., NIOSH
Hazard Section, Cincinnati, Ohio, July 26, 1988. Unpublished NIOSH
data on worker exposures to 1,3-butadiene.
18. Printouts received by Buchanan, S. K., Radian Corporation, from Seta,
J., NIOSH Hazard Section, Cincinnati, Ohio, July 1987. National
Occupational Hazard Surveys, extracted data from 1972-1974 and
1981-1983.
*
19. U. S. Environmental Protection Agency. 1987 Toxic Chemical Release
Inventory (SARA 313) Data Base. Office of Toxic Substances,
Washington, DC. Current as of June 1989.
112
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SECTION 8
SOURCE TEST PROCEDURES
1,3-Butadiene emissions can be measured by two methods: (1) EPA
Reference Method 18, which was announced In the Federal Register on
October 18, 1983;l and (2) NIOSH Analytical Method 1024 published In the
NIQSH Manual of Analytical Methods on August 15, 1987.2 EPA Reference
Method 18 applies to the sampling and analysis of approximately 90 percent
of the total gaseous organics emitted from an industrial source; whereas,
NIOSH Method 1024 applies specifically to the collection and analysis of
1,3-butadiene. A third method has been developed and validated specifically
to measure butadiene in vehicle exhaust. Because of the more limited scope
of application, no discussion of this method, a gas chromatography/f1ame
ionization detector (6C/FID)-based method, will be presented.
EPA REFERENCE METHOD 18
In Method 18, a sample of the exhaust gas to be analyzed is drawn into
a Tedlar® or aluminized Mylar* bag as shown in Figure 15. The bag is placed
inside a rigid, leakproof container and evacuated. The bag is then
connected by a Teflon* sampling line to a sampling probe (stainless steel,
Pyrex® glass, or Teflon*) at the center of the stack. The sample is drawn
into the bag by pumping air out of the rigid container.
The sample is then analyzed by gas chromatography (GC) coupled with
flame ionization detection (FID). Based on recent field and laboratory
validation studies, the recommended time limit for analysis is within
4
30 days of sample collection. One recommended column is the 1.82 meter
(6 feet) "Supelco Porapak QS. However, the GC operator should select the
column and GC conditions that provide good resolution and minimum analysis
time for 1,3-butadiene. Zero helium or nitrogen should be used as the
carrier gas at a flow rate that optimizes the resolution.
113
-------
c
'co
O5
"5.
CO
CO
O3
(0
CD
•o
03
4-t
CO
o>
03
3
O5
114
-------
The peak areas corresponding to the retention times of 1,3-butadiene
are measured and compared to peak areas for a set of standard gas mixtures
to determine the 1,3-butadiene concentrations. The detection limit of this
method ranges from about 1 ppm to an upper limit governed by the FID
saturation or column overloading. However, the upper limit can be extended
by diluting the stack gases with an inert gas or by using smaller gas
sampling loops.
Recent work by EPA's Atmospheric Research and Exposure Assessment
Laboratory has produced a modified version of Method 18 for stationary
source sampling. One difference is in the sampling rate which is reduced
to allow collection of more manageable gas volumes. The second introduces a
filtering medium to remove entrained liquids; this improves the butadiene
quantitation precision.
Two other changes involve the analytical procedure. The first uses
picric acid in a second column (2 m x 1/8" stainless steel column, 0.19%
picric acid on 80/100 mesh Carbopak C) to minimize the interference by
butane and butene isomers which are also present in the stream. The second
uses a backflush-to-vent configuration to remove any high boiling compounds
that have been collected before they reach the picric acid column. These
modifications allow more accurate quantitiation of butadiene to be performed
in a short time period than with Method 18.
NIOSH METHOD 1024
In the NIOSH method, samples are collected with adsorbent tubes
containing charcoal which has been washed and coated with 10 percent by
weight 4-tert-butylcatechol (TBC-charcoal), a chemical known to inhibit the
polymerization of 1,3-butadiene. Three-liter air samples should be
collected with the use of a personal sampling pump at a flow rate of
0.05 L/minute.2'7
115
-------
Samples are desorbed with carbon disulfide and analyzed by GC equipped
with an FID and a column capable of resolving 1,3-butadiene from the solvent
front and other interferences. The column specified in NIOSH Method 1024 is
a 50 m x 32 mm internal diameter (10) fused-silica, porous-layer,
open-tubular (PLOT) column coated with aluminum oxide and potassium chloride
2
(A1203/KC1). Degradation of compound separation may be eliminated by using
a back-flushable precolumn [i.e., 10 m x 0.5 mm ID fused-silica (CP Wax 57
CB)]. The precolumn allows light hydrocarbons to pass through, but water,
methylene chloride, and polar or high boiling components are retained and
2 6
can be backflushed. '
The amount of 1,3-butadiene in a sample is obtained from the
calibration curve in units of micrograms per sample. Collected samples
are sufficiently stable to permit six days of ambient sample storage before
analysis. If samples are refrigerated, they are stable for 18 days.
Butadiene can dimerize during handling and storage. The rate of
dimerization is a function of temperature, increasing with increasing
temperature. Consequently, samples should be stored at low temperatures.
This procedure is applicable for monitoring 1,3-butadiene air
concentrations ranging from 0.16 ppm to 36 ppm. The GC column and operating
conditions should provide good resolution and minimum analysis time.
116
-------
REFERENCES FOR SECTION 8
1. Method 18: Measurement of Gaseous Organic Compound Emissions by Gas
Chromatography. Federal Register 48(202):48344-48361.
October 18, 1983.
2. U. S. Department of Health, Education, and Welfare. NIOSH Manual of
Analytical Methods, 3rd ed., Volume 1. National Institute for
Occupational Safety and Health, Cincinnati, Ohio. 1984. pp. 1024-1
to 1024-9.
3. U. S. Environmental Protection Agency. Butadiene Measurement
Methodology. EPA-460/3-88-005 (NTIS PB89-104293/AS). Office of Air
and Radiation, Ann Arbor, Michigan. August 1988.
4. Personal Communication. Moody, T. K., Radian Corporation, with
Pau, J., U. S. EPA/Emissions Monitoring Systems Laboratory, June 6,
1988. Discussion of EPA Reference Methods 18 and 23.
5. Acurex Corporation. Acurex Interim Report: Development of Methods for
Sampling 1,3-Butadiene. 1987. pp. 4-1 through 4-18.
6. U. S. Environmental Protection Agency. Sampling and Analysis of
Butadiene at a Synthetic Rubber Plant. Project Report prepared by
Entropy Environmentalists, Inc., EPA Contract No. 68-02-4442, for
J. Pau, Atmospheric Research and Exposure Assessment Laboratory,
Quality Assurance Division. October 1988. pp. 3-5.
7. Hendricks, W. D., and G. R. Schultz. A Sampling and Analytical Method
for Monitoring Low ppm Air Concentrations of 1,3-Butadiene. Appl. Ind.
Hyg. 1(4): 186-190. 1986.
117
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APPENDIX A
SAMPLE CALCULATIONS FOR EQUIPMENT LEAKS
-------
-------
APPENDIX A
SAMPLE CALCULATIONS FOR EQUIPMENT LEAKS
An estimate of equipment leak emissions of butadiene depends on the
equipment type (e.g., pump seals, flanges, valves, etc.), the associated
emission factor, and the number of process components. For batch processes,
the hr/yr that butadiene actually flows through the component is estimated
from the reported percent of the year the equipment operates. For
continuous processes, butadiene is assumed to flow through the equipment
8,760 hours per year.
The annual uncontrolled emission rate of butadiene from a specific
equipment type is estimated by multiplying the following:
/ \ / weight % \ /component \ /# hours/yr\
(# equipment] x (butadiene in] x f emission 1 x ( butadiene ]
\ components/ \ the stream/ \ factor / \ in service/
Component emission factors from Table 8 include controls in use by the
facilities studied; therefore, SOCMI emission factors are used to estimate
uncontrolled emissions. The resulting emissions estimate is adjusted for
controls, where applicable, using the control efficiencies presented in
Tabl'e 10 of the text.
Sample calculations are provided below to demonstrate the estimation
procedure using information from Table A-l. Assuming continuous operation:
Emissions from Pump Seals
a) Mechanical
[(9 x 0.025) + (2 x 0.18)] x 0.0494 x 8,760 = 253 kg/yr
A-3
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b) Double Mechanical
(1 x 0.025) x 0 x 8,760 - 0 kg/yr
c) Total Uncontrolled and Controlled - 253 kg/yr
Emissions from Pressure Relief Devices
a) Gas + Liquid - uncontrolled
[(13 x 0.025) + (50 x 0.075) + (2 x 0.18)] x 0.104 x 8,760
- 4,041 kg/yr
b) Gas + Liquid - controlled
4,041 x [1 - (51/100)] - 1,980 kg/yr
A-5
-------
APPENDIX B
FACILITY-SPECIFIC EMISSIONS DATA
FROM EPA SECTION 114 RESPONSES
-------
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APPENDIX B
FACILITY-SPECIFIC EMISSIONS DATA
FROM EPA SECTION 114 RESPONSES
Tables B-l through B-25 contain the capacity and emissions data that
form the basis for the emission factor ranges and ranges of annual emissions
presented in the preceding sections. Capacity data were compiled from
responses to Section 114 requests or literature values if available. Most
of the emissions data are from responses to Section 114 requests in 1984.
Inconsistencies with the text are due to facility changes in ownership
and/or in the production process since 1984. The emission values,
therefore, may no longer reflect the current status of the industry.
Furthermore, reported emissions were not supplied for every emission point
*
identified. Nor were all emission points identified by each facility.
Emission factors for each emission point were calculated by dividing
the reported emissions by the facility's capacity, modified to reflect
actual production. In instances where the use of facility production
capacity in an emission factor might reveal company confidential
information, the emissions data were not used to calculate the ranges. In
the absence of facility-reported capacity values, literature values may have
been used.
Equipment leak emission estimates were derived from 1984 data supplied
by fac'ilities in Section 114 responses. Us'ing the procedure described in
Appendix A and average CMA emission factors, ranges of annual emissions were
calculated. Equipment count data for the miscellaneous category were
unavailable, therefore estimates are based on the SOCMI emission factors as
reported in the summary memoranda.
EPA is now actively collecting and receiving more recent information on
emissions of 1,3-butadiene from industrial sources. These data could not be
analyzed in sufficient time for their inclusion in this report, but will be
evaluated for a potential future update. One observation is that the data
becoming available indicate a higher level of control at facilities than
previously was employed.
B-3
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B-5
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TABLE B-3. SUMMARY OF BUTADIENE EMISSIONS (1987) FROM EQUIPMENT
LEAKS AT NINE PRODUCTION FACILITIES2
Equipment Component
Pumps - liquid
Compressors
Flanges
Valves - gas
Valves - liquid
Pressure relief devices
Open-ended lines
Sample points
Number of
Components
376
17
47,277b
6,315
23,233
428
1,744
40
79,430b
Emissions
(Mg/yr)
67
0.0002
46
22
230
41
0.67
0.34
410
(tons/yr)
74
0.0002
51
24
260
45
0.73
0.37
460
aAssumes 80 percent of production capacity (taken as 8760 hours of operations
per year). Emissions rounded to two significant figures.
Although only 11,428 flanges were included in the study, a ratio of 1.6:1
flanges:valves is generally accepted. The total number of flanges upon which
the emission estimate is based is, therefore, [(6,315 + 23,233) x 1.6] =
47,277.
cEmission factor was taken from reference 2, p.5-16.
3-6
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B-7
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TABLE B-5. STYREJB-BUTADIEHE ELASTOMER AMD LATEX PRODUCTION FACILITIES
FOR WHICH 1984 EMISSIONS DATA ARE AVAILABLE3
Company
Elastomer
American Synthetic
BW r?4«M«4«»4 jkh^
• f . wOOQcLcn
Copolymer Rubber
Firestone
GenCorp
Goodyear
Oniroyal0
Latex
e
Borg~Wamer
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
Dow Chemical
GenCorp
e
Goodyear
Goody* at
W. R. Grace
Polyaar
Raichhold (DE)
Heichhold (GA)
Unocal
Location
Louisville, KY
Port Heches , TX
Baton Rouge, LA
Lake Charles, LA
Odessa, TX
Houston, TX
Port Heches, TX
UA«K4nff^nn UV
wasnuigbon , ™*
Dalton, GA
Freeport , TX
Gates Ferry, CT
Mi *41 xnA MT
ruoxanu, rx^
Pittsburgh, CA
Mogadore , OH
AI__-___ f\r]
AKron , \ja
Calhoun, GA
Owenaboro, KY
Chattanooga, TN
Chesvold, QE
KensLngcon, GA
La Mirada, CA
Capacity (Mg/yr)
In 198**
100,000
d
211,000
120,000
87,000
183,000
60,000
3,000
152,000
59,000
53,000
18,000
Weight for elastomer is dry weight.
Facility vas oethballed In 1984.
3.5. Goodrich and Uniroyal are now Amerlpol Synpol.
* --* means company confidential.
Facility operating status in 1988 unknown.
B-8
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B-10
-------
TABLE B-7. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT LEAKS
AT SB COPOLYMER PRODUCTION FACILITIES2'3
Company
El astomer
Facility A
Facility B
Facility C
Facility D
Facility E
Facility F
Facility G
Latex
Facility H
Facility. I
Faciloty J •
Facility K
Facility L
Facility M
Facility N
Facility 0
Facility P
Facility Q
Facility R
Facility T
Uncontrolled
Emissions
(Mg/Yr)a
5.6
7.7
13C
3.6
67
21C
13d
14
4.5
1.4
0.89
2.6
1.9
5.3
4.2
4.3
0.10
13
2.0
Control Status
PRDs vented to a flare
Rupture discs for PRDs
Rupture discs
Rupture discs and flare for PRDs
None reported
Rupture discs and flare for PRDs
Most PRDs have rupture discs vented
None reported
None reported
None reported
None reported
Some rupture discs
Rupture discs
None reported
Rupture discs for PRDs
None reported
None reported
Some rupture discs
Most PRDs have rupture discs
Calculated using 1984 equipment counts and average CMA emission factor.
Emissions rounded to two significant figures.
DPRDs= Pressure relief devices.
"The emissions are for both SB copolymer and nitrile rubber production.
The emissions are for both SB copolymer and polybutadiene production.
8-11
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TABLE B-9. POLYBUTADIENE PRODUCTION FACILITIES FOR.
WHICH 1984 EMISSIONS DATA ARE AVAILABLE4
Capacity (Mg/Yr)
Company Location in 1985
American Synthetic Rubber Louisville, KY 63,000a
Arco Chemical Channel view, TX 6,800
Borg-Warner Ottawa, IL c
Firestone Orange, TX )
d [ 110,000a
Firestone Lake Charles, LA )
Goodyear Beaumont, TX c
Phillips Borger, TX 64,000a
Polysar Orange, TX c
aValue taken from the literature.
Facility operating status in 1988 unknown.
cCompany confidential.
Facility coproduces SBS elastomer and polybutadiene rubber, but is
primarily dedicated to SB elastomer.
8-14
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B-15
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TABLE B-ll. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT LEAKS
AT POLYBUTADIENE PRODUCTION FACILITIES2'4
Uncontrolled
Company Emissions (Mg/Yr)
Facility A 3.7
Facility B 5.3
Facility D 29
Facility E 9.5
Facility F 5.2
Facility G 4.4
Calculated using 1984 equipment counts and average CMA emission factors,
Emissions rounded to two significant figures.
B-16
-------
TABLE B-12. BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES AT
POLYBUTADIENE PRODUCTION FACILITIES (Mg/yr)a'4
Source
Company Wastewater Solid Waste Waste Treatment
Facility B --- 0 Landfill
Facility C 0 —a Activated sludge
Facility F 19.3 --- Lagoon
facility lists as a source but provides no data.
"---" means no information available on the source.
B-17
-------
TABLE B-13. ADIPONITRILE PRODUCTION FACILITIES FOR WHICH
1984 EMISSIONS DATA ARE AVAILABLE5
Company Capacity (Mg/yr) in 1984
Facility A 210,000a
Facility B 132,900
aValue taken from the literature.
B-18
-------
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B-19
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TABLE B-15. BUTADIENE EMISSIONS (1984) FROM EQUIPMENT
LEAKS AT ADIPONITRILE PRODUCTION FACILITIES2'5
Uncontrol1ed
Emissions
Company (Mg/yr) Controls
Facility A 4.8 Ambient monitoring,
double mechanical
seals, some PRDs
routed to a flare.
Facility B 2.5 Quarterly LDAR,d
ambient monitoring,
double mechanical
seals.
Calculated using 1984 equipment counts and average CMA emission factors.
Emissions rounded to two significant figures.
Ambient monitoring in the vicinity is used to detect elevated VOCs,
potentially indicating leaks.
cPRDs means pressure relief devices.
LDAR means leak detection and repair program.
B-20
-------
TABLE B-16. BUTADIENE EMISSIONS (1984) FROM SECONDARY SOURCES AT
ADIPONITRILE PRODUCTION FACILITIES5
Uncontrolled
Company Source Description Emissions (Mg/yr)
Facility A
Waste tank
2.0
a
blowdown water
Facility B Sump tankb
b
Waste liquids
Wastewater 0.9
a"---" means not reported. Value taken from the literature.
Both sources are routed to a boiler with 99.9 percent reduction
efficiency.
B-21
-------
TABLE B-17. CHLOROPRENE/NEOPRENE PRODUCTION FACILITIES FOR WHICH
1984 EMISSIONS DATA ARE AVAILABLE8
Company Capacity (Mg/yr) in 1985a
Facility A 34,000
Facility B 43,000
aValues taken from the literature.
B-22
-------
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B-23
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TABLE B-19. ACRYLONITRILE-BUTAOIENE-STYRENE RESIN PRODUCTION FACILITIES
FOR WHICH 1984 EMISSIONS DATA ARE AVAILABLE7
Capacity (Mg/Yr)
Company Location in 1985a
Goodyear Akron, OH 150
Monsanto Addyston, OH 161,000
Monsanto Muscatine, IA 52,200
aValues taken from the literature.
Goodyear coproduces ABS with nitrile elastomer. About 3 percent is
dedicated to production.
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TABLE B-21. NITRILE ELASTOMER PRODUCTION FACILITIES FOR
WHICH 1984 EMISSIONS DATA ARE AVAILABLE7
Capacity
(Mg/Yr dry rubber
Company Location or latex) in 1985
B. F. Goodrich Akron, OH Oa
Copolymer Baton Rouge, LA 6,800
Goodyear Houston, TX 16,000
Goodyear0 Akron, OH 5,000
Sohiod Lima, OH ---e
Uniroyal Chemical Co. Painesville, OH 16,300
aB. F. Goodrich closed its 14,000 Mg/yr NBR facility in 1983. Facility
still produces 7,600 Mg/yr of vinyl pyridine.
Value taken from the literature.
cFacility also produces about 150 Mg/yr of A8S copolymer (3 percent of
production.
Facility operating status in 1988 unknown.
e"—" means company confidential.
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-------
REFERENCES FOR APPENDIX B
1. Memorandum from K. Q. Kuhn and R. A. Uassel, Radian Corporation, to
the Butadiene Source Category Concurrence File, March 25, 1986.
Estimate of 1,3-Butadiene Emissions from Production Facilities and
Emissions Reductions Achievable with Additional Controls.
2. Randall, J. L. et al., Radian Corporation. Fugitive Emissions from the
1,3-butadiene Production Industry: A Field Study. Final Report.
Prepared for the 1,3-Butadiene Panel of the Chemical Manufacturers
Association. April 1989. p. 5-11.
3. Memorandum from R. A. Wassel and K. Q. Kuhn, Radian Corporation to the
Butadiene Source Category Concurrence File, April 8, 1986. Estimates
of 1,3-Butadiene Emissions from Styrene-Butadiene Copolymer Facilities
and Emissions Reductions Achievable with Additional Controls.
4. Memorandum from E. P. Epner, Radian Corporation, to the Butadiene
Source Category Concurrence File, March 27, 1986. Estimates of
1,3-Butadiene from Polybutadiene Facilities and Emissions Reductions
Achievable with Additional Controls.
5. Memorandum from K. Q. Kuhn and R. C. Burt, Radian Corporation, to the
Butadiene Source Category Concurrence File, December 12, 1986.
Estimates of 1,3-Butadiene Emissions from Miscellaneous Sources and
Emissions Achievable with Candidate NESHAP Controls.
6. Memorandum from E. P. Epner, Radian Corporation, to L. B. Evans,
U. S. EPA/Chemicals and Petroleum Branch, December 23, 1985. Estimates
of 1,3-Butadiene Emissions from Neoprene Facilities and Emissions
Reductions Achievable with Additional Controls.
7. Memorandum from R. Burt and R. Howie, Radian Corporation, to
L. B. Evans, EPA/Chemicals and Petroleum Branch, January 29, 1986.
Estimates of Acrylonitrile, Butadiene, and Other VOC Emissions and
Controls for ABS and NBR Facilities'.
8. Telecon. Buchanan, S. K., Radian Corporation, with Urig, E.
(July 25, 1988) and Lewis, T. (July 26 1988), B. F. Goodrich.
Process description and emissions estimates.
9. U. S. Department of Health and Human Services. Industrial Hygiene
Survey Report of Phillips Chemical Company, Philtex Plant, Borger,
Texas. DHHS (NIOSH) Publication No. 1W/147.23 (PBB86-222395).
National Institute for Occupational Safety and Health, Cincinnati,
Ohio. 1986 (August 7, 1985 Survey).
B-31
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TECHNICAL REPORT DATA
(Pleau read Instructions on lite reverse before completing)
1. REPORT NO.
EPA-450/2-89-Q21
3. RECIPIENT'S ACCESSION NO.
4. TITLE ANO SUBTITLE
Locating And Estimating Air Emissions From Sources
Of 1,3-Butadiene
S. REPORT DATE
December 1989
6. PERFORMING ORGANIZATION CCOE
7. AUTHOR(S)
Susan K. Buchanan
8. PERFORMING ORGANIZATION REPORT NO
9. PERFORMING ORGANIZATION NAME ANO AOORESS
Radian Corporation
Post Office Box 13000
Research Triangle Park, North Carolina 27709
10. PROGRAM ELEMENT NO.
lirCONTHACT/GRANT NO.
68-02-4392
12. SPONSORING AGENCY NAME ANO AOORESS
Air Quality Management Division
OAR, OAQPS, AQMD, PCS (MD-15)
Noncriteria Pollutant Programs Branch (MD-15)
Research Triangle Park, North Carolina 27711
13. TYPE OF REPORT ANO PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
EPA Project Officer: Anne A. Pope
16. ABSTRACT
To assist groups interested in inventorying air emissions of various potentially
toxic substances, EPA is preparing a series of documents such as this to compile
available information on sources and emissions of these substances. This document
deals specifically with 1,3-butadiene. Its intended audience includes Federal,
State and local air pollution personnel and others interested in locating potential
emitters of 1,3-butadiene and in making gross estimates of air emissions therefrom.
This document presents information on (1) the types of sources that nay emit
1,3,-butadiene, (2) process variations and release points that nay be expected
within these sources, and (3) available emissions information indicating the
potential for 1,3-butadiene releases into the air from each operation.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.loeNTIFIERS/OPEN ENDED TERMS c. COSATI Field/Croup
1,3-Butadiene
Air Emissions Sources
Locating Air Emission Sources
Toxic Substances
18. DISTRIBUTION STATEMENT
Unlimited
19. SECURITY CLASS / Tins Report/
Unclassified
21. NO. OF PAGES
166
20. SECURITY CLASS (T
Unclassified
22. PRICE
EPA Form 2220-1 (R«». 4-77) PREVIOUS EDITION is OBSOLETE
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